CN104600389A - Method for recycling metal from spent lithium ion battery of lithium manganate anode material - Google Patents

Abstract

The invention relates to a method for recycling metal from a spent lithium ion battery of a lithium manganate positive material. The method comprises the following steps of discharging the spent lithium ion battery, disassembling or collecting anode scraps and positive fragments so as to obtain waste positive pieces, and roasting, dissolving and filtering the waste positive pieces so as to obtain waste lithium manganate powder; and roasting after mixing the waste lithium manganate powder with potassium hydrogen sulphate according to a certain proportion, leaching a roasted product by using water, then, filtering after adding potassium carbonate solution into the solution, and carrying out ball milling, replenishing a certain amount of lithium carbonate into filter residues, pressing the filter residues and putting the pressed filter residues into a resistance furnace to roast, so as to obtain the lithium manganate positive material again. Components in the filtrate are adjusted by using sulphuric acid; and crystallized potassium hydrogen sulphate can be recycled.

Description

Method for recovering metal from waste lithium ion battery of lithium manganate cathode material

technical field

The invention relates to the technology of recovering metals from waste lithium ion batteries using lithium manganate as positive electrode material.

Background technique

Lithium-ion batteries are a new generation of secondary batteries developed rapidly in the 1990s, and are widely used in small portable electronic communication products and electric vehicles. According to statistics, in 2009, the output of lithium-ion batteries in my country reached 1.87 billion, and in 2010, the output of lithium-ion batteries in my country reached 2.68 billion. Since the service life of lithium-ion batteries is generally 2-3 years, the problems of environmental pollution and resource waste caused by discarded lithium-ion batteries have become increasingly prominent. The problem of how to properly dispose of discarded lithium-ion batteries cannot be ignored. The recycling and reuse of resources such as Co, Ni, Mn, Li, Al, and Cu in waste lithium-ion batteries not only overcomes the environmental pollution caused by the disposal of waste lithium-ion batteries by discarding methods, but also enables the recycling of limited resources. It not only has great economic benefits, but also has great significance in environmental protection.

The positive electrode material used in lithium-ion batteries is one of the key materials for manufacturing lithium-ion batteries, and occupies a core position in lithium-ion batteries. At present, most of the positive electrode materials of lithium-ion batteries use Co-based materials, but because Co is a rare metal, its quantity is small and expensive, which restricts the large-scale development of lithium-ion batteries. Manganese is rich in resources, cheap, low toxicity, and easy to recycle. Various lithium-intercalated lithium-manganese oxides have become the cathode materials for lithium-ion batteries that have attracted much attention. Lithium manganese oxide (LiMn ₂ O ₄ ) cathode material has great potential in lithium ion cathode materials, and has been used as the cathode active material in lithium ion power batteries and large energy storage batteries.

At present, there are methods for recovering metal from waste lithium ion batteries using lithium manganate as positive electrode material: patent [CN201410280343] discloses a method for preparing lithium nickel manganese oxide from waste lithium manganate batteries, by using sulfuric acid and peroxidation Lithium manganese oxide (LiNi _0.5 Mn _1.5 O ₄ ). Patent [CN201410246379] reports a method for recovering manganese and copper resources from manganese-based waste lithium-ion batteries, which continuously adopts acid-dissolution method, alkali-dissolution method, precipitation method, vibrating sieve screening method, flotation separation method or ultrasonic oscillation A solution containing Cu ²⁺ and Mn ²⁺ was obtained by the method, and then electrolytic operation was performed to obtain MnO ₂ and Cu. Patent [CN201310646706] discloses a method for preparing nickel-manganese hydroxide from waste power batteries. A mixed solution containing nickel and manganese is obtained by dissolving the waste nickel manganate lithium positive electrode material with at least one of hydrochloric acid, sulfuric acid and nitric acid, adding nickel acetate or nickel chloride or nickel sulfate, manganese chloride or Manganese sulfate or manganese acetate, glycerol or ethylene glycol or 1,2,4-butanetriol or 1,2-propanediol or 1,3-propanediol, and then adjust the pH value of the solution with sodium hydroxide and ammonia water respectively, After heating and dissolving-microwave reaction cooling-filtering-washing-drying, the nickel manganese hydroxide is obtained. Patent [CN201310630619] discloses a method for preparing lithium manganate positive electrode material using waste lithium ion batteries as raw materials, successively using citric acid solution and hydrogen peroxide solution to dissolve lithium manganate obtained from waste lithium ion batteries, and then pouring them into the solution Add lithium nitrate or lithium acetate or lithium sulfate, manganese nitrate or manganese acetate or manganese sulfate to adjust the molar ratio of Li to Mn in the solution, adjust the pH value of the solution with ammonia water to obtain a gel, and then undergo aging-drying-pre-calcination-calcination After that, lithium manganate cathode material is obtained. Patent [CN201310630768] reports a method for dissolving the positive electrode material of waste lithium-ion batteries, using malic acid solution and hydrogen peroxide solution to dissolve the lithium manganate positive electrode material obtained from waste lithium-ion batteries, that is, the waste lithium manganate is completed Dissolution process of cathode material. Patent [CN201210017163] discloses a method of using pyrometallurgical technology to use lithium manganate waste lithium-ion batteries and scrap iron as raw materials to manufacture ferromanganese alloys. Patent [CN201010141128] discloses a method for recovering valuable metals from waste lithium manganate batteries. After the waste battery is broken, use N,N-dimethylformamide, N-methylpyrrolidone, one or more mixed solvents in tetrahydrofuran to soak the electric core to obtain waste lithium manganese oxide, and use inorganic acid (36wt) that has added hydrogen peroxide % hydrochloric acid, 68wt% nitric acid, 98wt% sulfuric acid (one or more mixed acid solutions) mixed solution to dissolve waste lithium manganate, adjust the pH value of the solution twice with NaOH and ammonia water to obtain MnO ₂ , add sodium carbonate Lithium carbonate was obtained after the solution was precipitated. Patent [CN200910116656] reports a method and application of recovering MnO ₂ from waste lithium manganese oxide battery cathode materials, using sulfuric acid, hydrochloric acid, nitric acid or normal pressure acid leaching waste lithium manganate cathode materials to obtain λ-MnO ₂ , or α-/β-/γ-MnO ₂ is obtained by hydrothermal acid leaching waste lithium manganate cathode material. An Hongli et al. reported the recovery of main chemical elements of lithium manganate waste power lithium-ion batteries in "Journal of Peking University (Natural Science Edition)" Vol.42, Special Issue, Dec. 2006, 83-86, using 2mol/ The mixed solution of L HNO ₃ +1 mol/L H ₂ O ₂ has the best effect on acid-dissolving lithium manganate (LiMn ₂ O ₄ ), and the dissolution rate of lithium manganate is 100%. Yang Zeheng et al. reported the preparation of MnO ₂ and its electrochemical performance based on LiMn ₂ O ₄ as the positive electrode material of waste lithium-ion batteries in "Acta Chemical Society" Vol.62, No.1, November 2011, 3276-3281. λ-MnO _{2 nanoparticles were prepared by leaching waste LiMn 2 O 4} with 0.5 mol/L _{H 2} SO ₄ under pressure for 3 hours _; β-MnO ₂ nanorods were prepared from waste LiMn ₂ O ₄ for 24h. Peng Shantang and others reported the research results of the separation of lithium and manganese in lithium manganate (LiMn ₂ O ₄ ) by secondary oxidation-precipitation method in "Journal of Wuhan University of Technology" Vol.24, No.12, Dec.2002, 27-29 , dissolve lithium manganate with a mixed solution of nitric acid or hydrochloric acid or sulfuric acid with hydrogen peroxide added, and then add a certain amount of (NH ₄ ) ₂ S ₂ O ₈ and (NH ₄ ) ₂ CO ₃ , using secondary oxidation-precipitation method to prepare MnO ₂ and lithium carbonate.

In the method of recovering metals from the waste lithium ion battery with lithium manganate as the positive electrode material, sulfuric acid, nitric acid, citric acid and malic acid are used to dissolve the waste lithium manganate, which inevitably produces acid gas, NO _x waste gas and waste water with high inorganic acid content and organic acid content have caused serious secondary pollution to the atmospheric environment and water environment; the dissolution process has adopted a higher acid concentration and added hydrogen peroxide or ammonium persulfate, which The requirements for the anti-corrosion performance of recycling equipment are very high; the follow-up treatment process after dissolution is long, and the cost of regenerating waste lithium manganate is high. The method of using pyrometallurgical technology to use lithium manganate spent lithium-ion batteries as raw materials to manufacture ferromanganese alloys has the disadvantages of low added value of recycled products and high energy consumption in the regeneration process.

Contents of the invention

The purpose of the present invention is to provide a method for recovering metal from the waste lithium ion battery of lithium manganate cathode material.

The present invention is the method for reclaiming metal from the waste lithium ion battery of lithium manganate cathode material, and its steps are:

Step (1): Place the collected scrap lithium-ion battery with lithium manganate as positive electrode material in 0.1-1.0mol/L sodium hydroxide aqueous solution at room temperature for 1-3h discharge treatment; after discharge treatment, Disassemble the scrapped lithium-ion battery to obtain the positive electrode sheet; collect the positive electrode scraps and positive electrode scraps generated during the manufacturing process of the lithium-ion battery with lithium manganate as the positive electrode material to obtain the positive electrode sheet;

Step (2): Put the positive electrode sheet obtained in step (1) into the ceramic crucible according to the ratio of the mass of the positive electrode sheet to the volume of the ceramic crucible - g/mL is 1:10-1:15, Then place it in a resistance furnace from room temperature to raise the furnace temperature to 550°C at a rate of 5°C/min for 0.5-1h, then cut off the power of the resistance furnace, and cool it down to room temperature naturally; The ratio of the mass of the tablet to the volume of water-g/mL is 1:40-1:70. Put the positive electrode sheet into a container filled with water and stir for 5-30min. During the stirring process, the temperature of the water is 20-50°C. The stirring speed is 10-200r/min; after the stirring is stopped, sieve the mixture in the container with a 10-20 mesh screen, the sieve is aluminum foil, and the sieve is a solution containing positive active substances; the aluminum foil is washed with water for 1 -3 times, the aluminum foil was obtained by natural drying; the undersieve was subjected to suction filtration, and the filter was washed with water for 1-3 times to obtain the positive active material;

Step (3): Put the positive electrode active material obtained in step (2) into a ceramic crucible, and then place it in a resistance furnace to raise the furnace temperature to 500-700°C at a heating rate of 5°C/min and keep it warm for 0.5-3h , to obtain waste lithium manganate powder;

Step (4): Mix the waste lithium manganese oxide powder obtained in step (3) with potassium bisulfate at a mass ratio of -g/g of 1:0.2-1:1.2, then put them into a ceramic mortar and grind them thoroughly and mix them evenly , put the ground mixture into a ceramic crucible and cover it with a ceramic cover, then put it into a resistance furnace for roasting, raise the furnace temperature to 400-650°C at a heating rate of 3-10°C/min and keep it warm for 10-60min;

Step (5): After the calcination, the material in the crucible is leached with water at 20-50°C under the condition of stirring, the leaching time is 5-30min, and the solid-liquid ratio-g/mL is 1:10-1:50 ; Then heat the leachate to 95-98°C, slowly add 1.0-3.0mol/L potassium carbonate solution to the leachate, then filter, wash and dry the filter residue, analyze the content of Li and Mn in the filter residue, according to the molar ratio of lithium to manganese To meet the requirement of 0.525:1, add lithium carbonate to the filter residue, and then fully ball mill it in a ball mill, then press it under a pressure of 0.1-100MPa, put it into a clean ceramic crucible, and keep it in an air atmosphere at a constant temperature of 450°C for 4- After 7 hours, the temperature was raised to 750°C for 20 hours, and then slowly cooled to room temperature. The fired samples were pulverized, ground, and passed through a 400-mesh sieve to obtain lithium manganate cathode materials;

Step (6): Filter the solution obtained in step (5) to adjust the composition with concentrated sulfuric acid so that the pH of the solution is 0.5-1.0, and then crystallize in an evaporation crystallizer. The crystallization control conditions are vacuum degree 0.012-0.015MPa, temperature 120 -140°C, dry the crystals at 50-80°C for 0.2-3h to obtain potassium hydrogen sulfate, and return the obtained potassium hydrogen sulfate for use in step (4).

Compared with the prior art, the invention has the advantages of low recovery cost, easy operation, low requirement on equipment anticorrosion, excellent performance of the regenerated lithium manganate cathode material, and no secondary pollution during the regeneration process.

Detailed ways

The present invention is the method for reclaiming metal from the waste lithium ion battery of lithium manganate cathode material, and its steps are:

Step (1): Place the collected scrap lithium-ion battery with lithium manganate as positive electrode material in 0.1-1.0mol/L sodium hydroxide aqueous solution at room temperature for 1-3h discharge treatment; after discharge treatment, Disassemble the scrapped lithium-ion battery to obtain the positive electrode sheet; collect the positive electrode scraps and positive electrode scraps generated during the manufacturing process of the lithium-ion battery with lithium manganate as the positive electrode material to obtain the positive electrode sheet;

Step (2): Put the positive electrode sheet obtained in step (1) into the ceramic crucible according to the ratio of the mass of the positive electrode sheet to the volume of the ceramic crucible - g/mL is 1:10-1:15, Then place it in a resistance furnace from room temperature to raise the furnace temperature to 550°C at a rate of 5°C/min for 0.5-1h, then cut off the power of the resistance furnace, and cool it down to room temperature naturally; The ratio of the mass of the tablet to the volume of water-g/mL is 1:40-1:70. Put the positive electrode sheet into a container filled with water and stir for 5-30min. During the stirring process, the temperature of the water is 20-50°C. The stirring speed is 10-200r/min; after the stirring is stopped, sieve the mixture in the container with a 10-20 mesh screen, the sieve is aluminum foil, and the sieve is a solution containing positive active substances; the aluminum foil is washed with water for 1 -3 times, the aluminum foil was obtained by natural drying; the undersieve was subjected to suction filtration, and the filter was washed with water for 1-3 times to obtain the positive active material;

Step (3): Put the positive electrode active material obtained in step (2) into a ceramic crucible, and then place it in a resistance furnace to raise the furnace temperature to 500-700°C at a heating rate of 5°C/min and keep it warm for 0.5-3h , to obtain waste lithium manganate powder;

Step (4): Mix the waste lithium manganese oxide powder obtained in step (3) with potassium bisulfate at a mass ratio of -g/g of 1:0.2-1:1.2, then put them into a ceramic mortar and grind them thoroughly and mix them evenly , put the ground mixture into a ceramic crucible and cover it with a ceramic cover, then put it into a resistance furnace for roasting, raise the furnace temperature to 400-650°C at a heating rate of 3-10°C/min and keep it warm for 10-60min;

Step (5): After the calcination, the material in the crucible is leached with water at 20-50°C under the condition of stirring, the leaching time is 5-30min, and the solid-liquid ratio-g/mL is 1:10-1:50 ; Then heat the leachate to 95-98°C, slowly add 1.0-3.0mol/L potassium carbonate solution to the leachate, then filter, wash and dry the filter residue, analyze the content of Li and Mn in the filter residue, according to the molar ratio of lithium to manganese To meet the requirement of 0.525:1, add lithium carbonate to the filter residue, and then fully ball mill it in a ball mill, then press it under a pressure of 0.1-100MPa, put it into a clean ceramic crucible, and keep it in an air atmosphere at a constant temperature of 450°C for 4- After 7 hours, the temperature was raised to 750°C for 20 hours, and then slowly cooled to room temperature. The fired samples were pulverized, ground, and passed through a 400-mesh sieve to obtain lithium manganate cathode materials;

Step (6): Filter the solution obtained in step (5) to adjust the composition with concentrated sulfuric acid so that the pH of the solution is 0.5-1.0, and then crystallize in an evaporation crystallizer. The crystallization control conditions are vacuum degree 0.012-0.015MPa, temperature 120 -140°C, dry the crystals at 50-80°C for 0.2-3h to obtain potassium hydrogen sulfate, and return the obtained potassium hydrogen sulfate for use in step (4).

According to the method described above, the potassium hydrogen sulfate described in step (4) is: potassium hydrogen sulfate chemical product or potassium hydrogen sulfate obtained in step (6) or a mixture formed by mixing the two in any proportion.

According to the method described above, the mixing ratio of the spent lithium manganate powder and potassium bisulfate in step (4) is: the mass ratio -g/g is 1:0.2-1:1.2.

According to the above-mentioned method, the technical conditions for roasting in a resistance furnace in step (4) are: the heating rate is 3-10°C/min, the roasting temperature is 400-650°C, and the holding time is 10-60min.

According to the method described above, the ball milling time in step (5) is 0.5-2h, and the rotation speed is 200-500r/min.

Example 1:

Collect scrap lithium-ion batteries with lithium manganate as positive electrode material, place them in 1.0mol/L sodium hydroxide aqueous solution at room temperature for 2h discharge treatment; after discharge treatment, disassemble the scrap lithium-ion batteries to obtain Positive electrode sheet: according to the ratio (g/mL) of the mass of positive electrode sheet and the volume of ceramic crucible, positive electrode sheet is packed in the ratio of 1:15 in the ceramic crucible, is placed in box-type electric resistance furnace then and starts from room temperature with 5 ℃/mL The heating rate of min raised the furnace temperature to 550°C and kept it warm for 20 minutes, then cut off the power of the box-type resistance furnace, and cooled it to room temperature naturally; took out the roasted positive electrode sheet, and according to the ratio of the mass of the positive electrode sheet to the volume of water (g/ mL) is 1:50, put the positive electrode sheet into a container with water and stir it with an electric stirrer at a stirring speed of 50r/min for 20min, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, the mixture in the container Sieve with a 10-mesh sieve, the oversieve is aluminum foil, and the undersieve is a solution containing positive active substances; the aluminum foil is washed 3 times with water, and the aluminum foil is obtained by natural drying; the undersieve is subjected to suction filtration, and the oversieve is washed with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, then place it in a box-type resistance furnace to raise the furnace temperature to 600°C at a heating rate of 5°C/min and keep it for 30min to obtain waste manganese Lithium acid powder; Put the waste lithium manganate powder and the purchased potassium bisulfate chemical product into a ceramic mortar in a ratio of 1:0.75 by mass ratio (g/g), grind and mix evenly, and then put the ground mixture into Put it into a ceramic crucible and cover it with a ceramic cover and put it into a box-type resistance furnace to raise the temperature of the furnace to 650°C at a heating rate of 5°C/min and keep it warm for 30min; The water at 50°C was leached for 30 minutes at a solid-to-liquid ratio (g/mL) of 1:20; then the leachate was heated to 98°C, and 3.0mol/L potassium carbonate solution was slowly added to the leachate to produce a precipitate, which was filtered, After washing and drying, analyze the content of Li and Mn in the precipitate, add a certain amount of lithium carbonate to the precipitate according to the requirement that the molar ratio of lithium to manganese is 0.525:1, and then put it in the planetary ball mill at a speed of 400r/min Fully ball mill for 2 hours, then press it under the pressure of 5 MPa, put it into a clean ceramic crucible, keep the temperature at 450°C for 6 hours in the air atmosphere, then raise the temperature to 750°C and keep it for 20 hours, then slowly cool to room temperature, and the fired The sample is pulverized, ground, and passed through a 400-mesh sieve to obtain a lithium manganate positive electrode material; the solution obtained by filtering in the above steps is adjusted with concentrated sulfuric acid to make the pH value of the solution 1.0, and then crystallized in an evaporative crystallizer, and the crystallization control conditions are The vacuum degree is 0.015MPa, the temperature is 120°C, and the crystals are dried at 80°C for 2 hours to obtain potassium hydrogen sulfate.

Example 2

Collect scrap lithium-ion batteries with lithium manganate as positive electrode material, place them in 1.0mol/L sodium hydroxide aqueous solution at room temperature for 2h discharge treatment; after discharge treatment, disassemble the scrap lithium-ion batteries to obtain Positive electrode sheet: according to the ratio (g/mL) of the mass of positive electrode sheet and the volume of ceramic crucible, positive electrode sheet is packed in the ratio of 1:15 in the ceramic crucible, is placed in box-type electric resistance furnace then and starts from room temperature with 5 ℃/mL The heating rate of min raised the furnace temperature to 550°C and kept it warm for 20 minutes, then cut off the power of the box-type resistance furnace, and cooled it to room temperature naturally; took out the roasted positive electrode sheet, and according to the ratio of the mass of the positive electrode sheet to the volume of water (g/ mL) is 1:50, put the positive electrode sheet into a container with water and stir it with an electric stirrer at a stirring speed of 50r/min for 20min, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, the mixture in the container Sieve with a 10-mesh sieve, the oversieve is aluminum foil, and the undersieve is a solution containing positive active substances; the aluminum foil is washed 3 times with water, and the aluminum foil is obtained by natural drying; the undersieve is subjected to suction filtration, and the oversieve is washed with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, then place it in a box-type resistance furnace to raise the furnace temperature to 600°C at a heating rate of 5°C/min and keep it for 30min to obtain waste manganese Lithium acid powder; Put the waste lithium manganate powder and the purchased potassium bisulfate chemical product into a ceramic mortar in a ratio of 1:0.75 by mass ratio (g/g), grind and mix evenly, and then put the ground mixture into Put it into a ceramic crucible and cover it with a ceramic cover, put it into a box-type resistance furnace, raise the temperature of the furnace to 600°C at a heating rate of 5°C/min and keep it warm for 30min; The water at 50°C was leached for 30 minutes at a solid-to-liquid ratio (g/mL) of 1:20; then the leachate was heated to 98°C, and 3.0mol/L potassium carbonate solution was slowly added to the leachate to produce a precipitate, which was filtered, After washing and drying, analyze the content of Li and Mn in the precipitate, add a certain amount of lithium carbonate to the precipitate according to the requirement that the molar ratio of lithium to manganese is 0.525:1, and then put it in the planetary ball mill at a speed of 400r/min Fully ball mill for 2 hours, then press it under the pressure of 5 MPa, put it into a clean ceramic crucible, keep the temperature at 450°C for 6 hours in the air atmosphere, then raise the temperature to 750°C and keep it for 20 hours, then slowly cool to room temperature, and the fired The sample is pulverized, ground, and passed through a 400-mesh sieve to obtain a lithium manganate positive electrode material; the solution obtained by filtering in the above steps is adjusted with concentrated sulfuric acid to make the pH value of the solution 1.0, and then crystallized in an evaporative crystallizer, and the crystallization control conditions are The vacuum degree is 0.015MPa, the temperature is 120°C, and the crystals are dried at 80°C for 2 hours to obtain potassium hydrogen sulfate.

Example 3

Collect scrap lithium-ion batteries with lithium manganate as positive electrode material, place them in 1.0mol/L sodium hydroxide aqueous solution at room temperature for 2h discharge treatment; after discharge treatment, disassemble the scrap lithium-ion batteries to obtain Positive electrode sheet: according to the ratio (g/mL) of the mass of positive electrode sheet and the volume of ceramic crucible, positive electrode sheet is packed in the ratio of 1:15 in the ceramic crucible, is placed in box-type electric resistance furnace then and starts from room temperature with 5 ℃/mL The heating rate of min raised the furnace temperature to 550°C and kept it warm for 20 minutes, then cut off the power of the box-type resistance furnace, and cooled it to room temperature naturally; took out the roasted positive electrode sheet, and according to the ratio of the mass of the positive electrode sheet to the volume of water (g/ mL) is 1:50, put the positive electrode sheet into a container with water and stir it with an electric stirrer at a stirring speed of 50r/min for 20min, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, the mixture in the container Sieve with a 10-mesh sieve, the oversieve is aluminum foil, and the undersieve is a solution containing positive active substances; the aluminum foil is washed 3 times with water, and the aluminum foil is obtained by natural drying; the undersieve is subjected to suction filtration, and the oversieve is washed with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, then place it in a box-type resistance furnace to raise the furnace temperature to 600°C at a heating rate of 5°C/min and keep it for 30min to obtain waste manganese Lithium acid powder; Put the waste lithium manganate powder and the purchased potassium bisulfate chemical product into a ceramic mortar in a ratio of 1:0.75 by mass ratio (g/g), grind and mix evenly, and then put the ground mixture into Put it into a ceramic crucible and cover it with a ceramic cover, put it into a box-type resistance furnace, raise the temperature of the furnace to 500°C at a heating rate of 5°C/min and keep it warm for 30min; Water at 50°C was leached for 20 minutes at a solid-to-liquid ratio (g/mL) of 1:20; then the leachate was heated to 98°C, and 3.0mol/L potassium carbonate solution was slowly added to the leachate to produce a precipitate, which was filtered, After washing and drying, analyze the content of Li and Mn in the precipitate, add a certain amount of lithium carbonate to the precipitate according to the requirement that the molar ratio of lithium to manganese is 0.525:1, and then put it in the planetary ball mill at a speed of 400r/min Fully ball mill for 2 hours, then press it under the pressure of 5 MPa, put it into a clean ceramic crucible, keep the temperature at 450°C for 6 hours in the air atmosphere, then raise the temperature to 750°C and keep it for 20 hours, then slowly cool to room temperature, and the fired The sample is pulverized, ground, and passed through a 400-mesh sieve to obtain a lithium manganate positive electrode material; the solution obtained by filtering in the above steps is adjusted with concentrated sulfuric acid to make the pH value of the solution 1.0, and then crystallized in an evaporative crystallizer, and the crystallization control conditions are The vacuum degree is 0.015MPa, the temperature is 120°C, and the crystals are dried at 80°C for 2 hours to obtain potassium hydrogen sulfate.

Example 4

Collect scrap lithium-ion batteries with lithium manganate as positive electrode material, place them in 1.0mol/L sodium hydroxide aqueous solution at room temperature for 2h discharge treatment; after discharge treatment, disassemble the scrap lithium-ion batteries to obtain Positive electrode sheet: according to the ratio (g/mL) of the mass of positive electrode sheet and the volume of ceramic crucible, positive electrode sheet is packed in the ratio of 1:15 in the ceramic crucible, is placed in box-type electric resistance furnace then and starts from room temperature with 5 ℃/mL The heating rate of min raised the furnace temperature to 550°C and kept it warm for 20 minutes, then cut off the power of the box-type resistance furnace, and cooled it to room temperature naturally; took out the roasted positive electrode sheet, and according to the ratio of the mass of the positive electrode sheet to the volume of water (g/ mL) is 1:50, put the positive electrode sheet into a container with water and stir it with an electric stirrer at a stirring speed of 50r/min for 20min, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, the mixture in the container Sieve with a 10-mesh sieve, the oversieve is aluminum foil, and the undersieve is a solution containing positive active substances; the aluminum foil is washed 3 times with water, and the aluminum foil is obtained by natural drying; the undersieve is subjected to suction filtration, and the oversieve is washed with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, then place it in a box-type resistance furnace to raise the furnace temperature to 600°C at a heating rate of 5°C/min and keep it for 30min to obtain waste manganese Lithium acid powder; Put the waste lithium manganate powder and the purchased potassium bisulfate chemical product into a ceramic mortar in a ratio of 1:0.75 by mass ratio (g/g), grind and mix evenly, and then put the ground mixture into Put it into a ceramic crucible and cover it with a ceramic cover, put it into a box-type resistance furnace, raise the temperature of the furnace to 450°C at a heating rate of 5°C/min and keep it warm for 30min; Water at 50°C was leached for 20 minutes at a solid-to-liquid ratio (g/mL) of 1:20; then the leachate was heated to 98°C, and 3.0mol/L potassium carbonate solution was slowly added to the leachate to produce a precipitate, which was filtered, After washing and drying, analyze the content of Li and Mn in the precipitate, add a certain amount of lithium carbonate to the precipitate according to the requirement that the molar ratio of lithium to manganese is 0.525:1, and then put it in the planetary ball mill at a speed of 400r/min Fully ball mill for 2 hours, then press it under the pressure of 5 MPa, put it into a clean ceramic crucible, keep the temperature at 450°C for 6 hours in the air atmosphere, then raise the temperature to 750°C and keep it for 20 hours, then slowly cool to room temperature, and the fired The sample is pulverized, ground, and passed through a 400-mesh sieve to obtain a lithium manganate positive electrode material; the solution obtained by filtering in the above steps is adjusted with concentrated sulfuric acid to make the pH value of the solution 1.0, and then crystallized in an evaporative crystallizer, and the crystallization control conditions are The vacuum degree is 0.015MPa, the temperature is 120°C, and the crystals are dried at 80°C for 2 hours to obtain potassium hydrogen sulfate.

Example 5

Collect positive electrode scraps and positive electrode residues produced by the lithium ion battery manufacturing process with lithium manganate as the positive electrode material to obtain the positive electrode sheet; Put the positive electrode piece into a ceramic crucible, and then place it in a box-type resistance furnace to raise the temperature of the furnace to 550 °C at a rate of 5 °C/min from room temperature and keep it for 20 min. Room temperature; take out the positive electrode sheet after roasting, put the positive electrode sheet into a container filled with water according to the ratio of the mass of the positive electrode sheet to the volume of water (g/mL) of 1:50 and stir with an electric stirrer at 50r/min Stir at a high speed for 20 minutes, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, sieve the mixture in the container with a 10-mesh sieve, the sieve is aluminum foil, and the sieve is a solution containing positive active substances; Rinse with water 3 times, and obtain aluminum foil by natural drying; filter the undersieve, and wash the supernatant with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, and then place it in a box-type resistance furnace Make furnace temperature rise to 600 ℃ and be incubated 30min with the heating rate of 5 ℃/min in, obtain waste lithium manganate powder; Waste lithium manganate powder and the potassium bisulfate obtained in step (6) of the present invention are by mass ratio ( g/g) at a ratio of 1:1, put it into a ceramic mortar, grind and mix it evenly, then put the ground mixture into a ceramic crucible and cover it with a ceramic cover and put it in a box-type resistance furnace at a temperature of 5°C/min. The heating rate is to raise the furnace temperature to 450°C and keep it warm for 20min; after the calcination, the material in the crucible is leached with 40°C water for 30min at a solid-to-liquid ratio (g/mL) of 1:30 under stirring conditions; then Raise the temperature of the leachate to 95°C, slowly add 3.0mol/L potassium carbonate solution into the leachate to produce a precipitate, the obtained precipitate is filtered, washed, and dried, and the content of Li and Mn in the precipitate is analyzed, according to the molar ratio of lithium to manganese Add a certain amount of lithium carbonate to the sediment to meet the requirement of 0.525:1, then fully ball mill it in a planetary ball mill at a speed of 400r/min for 2 hours, then press it under a pressure of 5MPa, and put it into a clean ceramic crucible , keep the temperature at 450°C for 6 hours in an air atmosphere, then raise the temperature to 750°C for 20 hours, then slowly cool to room temperature, grind and grind the fired samples, and pass through a 400-mesh sieve to obtain the lithium manganate cathode material; filter the above steps The obtained solution was adjusted with concentrated sulfuric acid to make the pH value of the solution 1.0, and then crystallized in an evaporative crystallizer. The crystallization control conditions were vacuum degree of 0.015MPa and temperature of 120°C. The crystallized product was dried at 80°C and 2h to obtain potassium bisulfate .

Example 6

Collect positive electrode scraps and positive electrode residues produced by the lithium ion battery manufacturing process with lithium manganate as the positive electrode material to obtain the positive electrode sheet; Put the positive electrode piece into a ceramic crucible, and then place it in a box-type resistance furnace to raise the temperature of the furnace to 550 °C at a rate of 5 °C/min from room temperature and keep it for 20 min. Room temperature; take out the positive electrode sheet after roasting, put the positive electrode sheet into a container filled with water according to the ratio of the mass of the positive electrode sheet to the volume of water (g/mL) of 1:50 and stir with an electric stirrer at 50r/min Stir at a high speed for 20 minutes, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, sieve the mixture in the container with a 10-mesh sieve, the sieve is aluminum foil, and the sieve is a solution containing positive active substances; Rinse with water 3 times, and obtain aluminum foil by natural drying; filter the undersieve, and wash the supernatant with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, and then place it in a box-type resistance furnace Make furnace temperature rise to 600 ℃ and be incubated 30min with the heating rate of 5 ℃/min in, obtain waste lithium manganate powder; Waste lithium manganate powder and the potassium bisulfate obtained in step (6) of the present invention are by mass ratio ( g/g) at a ratio of 1:1, put it into a ceramic mortar, grind and mix it evenly, then put the ground mixture into a ceramic crucible and cover it with a ceramic cover and put it in a box-type resistance furnace at a temperature of 5°C/min. The heating rate is to raise the furnace temperature to 500°C and keep it warm for 20min; after the roasting is completed, the material in the crucible is leached with 40°C water under the condition of stirring for 30min at a solid-to-liquid ratio (g/mL) of 1:30; then Raise the temperature of the leachate to 95°C, slowly add 3.0mol/L potassium carbonate solution into the leachate to produce a precipitate, the obtained precipitate is filtered, washed, and dried, and the content of Li and Mn in the precipitate is analyzed, according to the molar ratio of lithium to manganese Add a certain amount of lithium carbonate to the sediment to meet the requirement of 0.525:1, then fully ball mill it in a planetary ball mill at a speed of 400r/min for 2 hours, then press it under a pressure of 5MPa, and put it into a clean ceramic crucible , keep the temperature at 450°C for 6 hours in an air atmosphere, then raise the temperature to 750°C for 20 hours, then slowly cool to room temperature, grind and grind the fired samples, and pass through a 400-mesh sieve to obtain the lithium manganate cathode material; filter the above steps The obtained solution was adjusted with concentrated sulfuric acid to make the pH value of the solution 1.0, and then crystallized in an evaporative crystallizer. The crystallization control conditions were vacuum degree of 0.015MPa and temperature of 120°C. The crystallized product was dried at 80°C and 2h to obtain potassium bisulfate .

Example 7

Collect positive electrode scraps and positive electrode residues produced by the lithium ion battery manufacturing process with lithium manganate as the positive electrode material to obtain the positive electrode sheet; Put the positive electrode piece into a ceramic crucible, and then place it in a box-type resistance furnace to raise the temperature of the furnace to 550 °C at a rate of 5 °C/min from room temperature and keep it for 20 min. Room temperature; take out the positive electrode sheet after roasting, put the positive electrode sheet into a container filled with water according to the ratio of the mass of the positive electrode sheet to the volume of water (g/mL) of 1:50 and stir with an electric stirrer at 50r/min Stir at a high speed for 20 minutes, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, sieve the mixture in the container with a 10-mesh sieve, the sieve is aluminum foil, and the sieve is a solution containing positive active substances; Rinse with water 3 times, and obtain aluminum foil by natural drying; filter the undersieve, and wash the supernatant with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, and then place it in a box-type resistance furnace Make furnace temperature rise to 600 ℃ and be incubated 30min with the heating rate of 5 ℃/min in, obtain waste lithium manganate powder; Waste lithium manganate powder and the potassium bisulfate obtained in step (6) of the present invention are by mass ratio ( g/g) at a ratio of 1:1, put it into a ceramic mortar, grind and mix it evenly, then put the ground mixture into a ceramic crucible and cover it with a ceramic cover and put it in a box-type resistance furnace at a temperature of 5°C/min. The heating rate is to raise the furnace temperature to 550°C and keep it warm for 20min; after the calcination, the material in the crucible is leached with water at 40°C for 30min at a solid-to-liquid ratio (g/mL) of 1:30 under stirring conditions; then Raise the temperature of the leachate to 98°C, slowly add 3.0mol/L potassium carbonate solution into the leachate to produce a precipitate, the obtained precipitate is filtered, washed, and dried, and the content of Li and Mn in the precipitate is analyzed, according to the molar ratio of lithium to manganese Add a certain amount of lithium carbonate to the sediment to meet the requirement of 0.525:1, then fully ball mill it in a planetary ball mill at a speed of 400r/min for 2 hours, then press it under a pressure of 5MPa, and put it into a clean ceramic crucible , keep the temperature at 450°C for 6 hours in an air atmosphere, then raise the temperature to 750°C for 20 hours, then slowly cool to room temperature, grind and grind the fired samples, and pass through a 400-mesh sieve to obtain the lithium manganate cathode material; filter the above steps The obtained solution was adjusted with concentrated sulfuric acid to make the pH value of the solution 1.0, and then crystallized in an evaporative crystallizer. The crystallization control conditions were vacuum degree of 0.015MPa and temperature of 120°C. The crystallized product was dried at 80°C and 2h to obtain potassium bisulfate .

Example 8

Collect positive electrode scraps and positive electrode residues produced by the lithium ion battery manufacturing process with lithium manganate as the positive electrode material to obtain the positive electrode sheet; Put the positive electrode piece into a ceramic crucible, and then place it in a box-type resistance furnace to raise the temperature of the furnace to 550 °C at a rate of 5 °C/min from room temperature and keep it for 20 min. Room temperature; take out the positive electrode sheet after roasting, put the positive electrode sheet into a container filled with water according to the ratio of the mass of the positive electrode sheet to the volume of water (g/mL) of 1:50 and stir with an electric stirrer at 50r/min Stir at a high speed for 20 minutes, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, sieve the mixture in the container with a 10-mesh sieve, the sieve is aluminum foil, and the sieve is a solution containing positive active substances; Rinse with water 3 times, and obtain aluminum foil by natural drying; filter the undersieve, and wash the supernatant with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, and then place it in a box-type resistance furnace Make furnace temperature rise to 600 ℃ and be incubated 30min with the heating rate of 5 ℃/min in, obtain waste lithium manganate powder; Waste lithium manganate powder and the potassium bisulfate obtained in step (6) of the present invention are by mass ratio ( g/g) at a ratio of 1:1, put it into a ceramic mortar, grind and mix it evenly, then put the ground mixture into a ceramic crucible and cover it with a ceramic cover and put it in a box-type resistance furnace at a temperature of 5°C/min. The heating rate is to raise the furnace temperature to 650°C and keep it warm for 20 minutes; after the roasting is completed, the material in the crucible is leached with 40°C water under the condition of stirring for 30 minutes at a solid-to-liquid ratio (g/mL) of 1:30; then Raise the temperature of the leachate to 98°C, slowly add 3.0mol/L potassium carbonate solution into the leachate to produce a precipitate, the obtained precipitate is filtered, washed, and dried, and the content of Li and Mn in the precipitate is analyzed, according to the molar ratio of lithium to manganese Add a certain amount of lithium carbonate to the sediment to meet the requirement of 0.525:1, then fully ball mill it in a planetary ball mill at a speed of 400r/min for 2 hours, then press it under a pressure of 5MPa, and put it into a clean ceramic crucible , keep the temperature at 450°C for 6 hours in an air atmosphere, then raise the temperature to 750°C for 20 hours, then slowly cool to room temperature, grind and grind the fired samples, and pass through a 400-mesh sieve to obtain the lithium manganate cathode material; filter the above steps The obtained solution was adjusted with concentrated sulfuric acid to make the pH value of the solution 1.0, and then crystallized in an evaporative crystallizer. The crystallization control conditions were vacuum degree of 0.015MPa and temperature of 120°C. The crystallized product was dried at 80°C and 2h to obtain potassium bisulfate .

Example 9

Collect scrap lithium-ion batteries with lithium manganate as positive electrode material, place them in 1.0mol/L sodium hydroxide aqueous solution at room temperature for 2h discharge treatment; after discharge treatment, disassemble the scrap lithium-ion batteries to obtain Positive electrode sheet: according to the ratio (g/mL) of the mass of positive electrode sheet and the volume of ceramic crucible, positive electrode sheet is packed in the ratio of 1:15 in the ceramic crucible, is placed in box-type electric resistance furnace then and starts from room temperature with 5 ℃/mL The heating rate of min raised the furnace temperature to 550°C and kept it warm for 20 minutes, then cut off the power of the box-type resistance furnace, and cooled it to room temperature naturally; took out the roasted positive electrode sheet, and according to the ratio of the mass of the positive electrode sheet to the volume of water (g/ mL) is 1:50, put the positive electrode sheet into a container with water and stir it with an electric stirrer at a stirring speed of 50r/min for 20min, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, the mixture in the container Sieve with a 10-mesh sieve, the oversieve is aluminum foil, and the undersieve is a solution containing positive active substances; the aluminum foil is washed 3 times with water, and the aluminum foil is obtained by natural drying; the undersieve is subjected to suction filtration, and the oversieve is washed with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, and then place it in a box-type resistance furnace to raise the furnace temperature to 600 ° C at a heating rate of 5 ° C / min and keep it for 30 min to obtain waste manganese Lithium acid powder; put the waste lithium manganate powder and the purchased potassium bisulfate chemical product into a ceramic mortar in a mass ratio (g/g) of 1:0.25, fully grind and mix evenly, and then put the ground mixture into Put it into a ceramic crucible and cover it with a ceramic cover, put it into a box-type resistance furnace, raise the temperature of the furnace to 600°C at a heating rate of 5°C/min and keep it warm for 30min; The water at 50°C was leached for 30 minutes at a solid-to-liquid ratio (g/mL) of 1:20; then the leachate was heated to 98°C, and 3.0mol/L potassium carbonate solution was slowly added to the leachate to produce a precipitate, which was filtered, After washing and drying, analyze the content of Li and Mn in the precipitate, add a certain amount of lithium carbonate to the precipitate according to the requirement that the molar ratio of lithium to manganese is 0.525:1, and then put it in the planetary ball mill at a speed of 400r/min Fully ball mill for 2 hours, then press it under the pressure of 5 MPa, put it into a clean ceramic crucible, keep the temperature at 450°C for 6 hours in the air atmosphere, then raise the temperature to 750°C and keep it for 20 hours, then slowly cool to room temperature, and the fired The sample was pulverized, ground, and passed through a 400-mesh sieve to obtain the lithium manganate positive electrode material; the solution obtained by filtering in the above steps was adjusted with concentrated sulfuric acid to make the pH value of the solution 1.0, and then crystallized in an evaporative crystallizer, and the crystallization control conditions were The vacuum degree is 0.015MPa, the temperature is 120°C, and the crystals are dried at 80°C for 2 hours to obtain potassium hydrogen sulfate.

Example 10

Collect scrap lithium-ion batteries with lithium manganate as positive electrode material, place them in 1.0mol/L sodium hydroxide aqueous solution at room temperature for 2h discharge treatment; after discharge treatment, disassemble the scrap lithium-ion batteries to obtain Positive electrode sheet: according to the ratio (g/mL) of the mass of positive electrode sheet and the volume of ceramic crucible, positive electrode sheet is packed in the ratio of 1:15 in the ceramic crucible, is placed in box-type electric resistance furnace then and starts from room temperature with 5 ℃/mL The heating rate of min raised the furnace temperature to 550°C and kept it warm for 20 minutes, then cut off the power of the box-type resistance furnace, and cooled it to room temperature naturally; took out the roasted positive electrode sheet, and according to the ratio of the mass of the positive electrode sheet to the volume of water (g/ mL) is 1:50, put the positive electrode sheet into a container with water and stir it with an electric stirrer at a stirring speed of 50r/min for 20min, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, the mixture in the container Sieve with a 10-mesh sieve, the oversieve is aluminum foil, and the undersieve is a solution containing positive active substances; the aluminum foil is washed 3 times with water, and the aluminum foil is obtained by natural drying; the undersieve is subjected to suction filtration, and the oversieve is washed with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, then place it in a box-type resistance furnace to raise the furnace temperature to 600°C at a heating rate of 5°C/min and keep it for 30min to obtain waste manganese Lithium acid powder; put the waste lithium manganate powder and the purchased potassium bisulfate chemical product into a ceramic mortar in a mass ratio (g/g) of 1:1.2, fully grind and mix evenly, and then put the ground mixture into Put it into a ceramic crucible and cover it with a ceramic cover, put it into a box-type resistance furnace, raise the temperature of the furnace to 600°C at a heating rate of 5°C/min and keep it warm for 20min; The water at 50°C was leached for 30 minutes at a solid-to-liquid ratio (g/mL) of 1:20; then the leachate was heated to 98°C, and 3.0mol/L potassium carbonate solution was slowly added to the leachate to produce a precipitate, which was filtered, After washing and drying, analyze the content of Li and Mn in the precipitate, add a certain amount of lithium carbonate to the precipitate according to the requirement that the molar ratio of lithium to manganese is 0.525:1, and then put it in the planetary ball mill at a speed of 400r/min Fully ball mill for 2 hours, then press it under the pressure of 5 MPa, put it into a clean ceramic crucible, keep the temperature at 450°C for 6 hours in the air atmosphere, then raise the temperature to 750°C and keep it for 20 hours, then slowly cool to room temperature, and the fired The sample is pulverized, ground, and passed through a 400-mesh sieve to obtain a lithium manganate positive electrode material; the solution obtained by filtering in the above steps is adjusted with concentrated sulfuric acid to make the pH value of the solution 1.0, and then crystallized in an evaporative crystallizer, and the crystallization control conditions are The vacuum degree is 0.015MPa, the temperature is 120°C, and the crystals are dried at 80°C for 2 hours to obtain potassium hydrogen sulfate.

Example 11

Collect positive electrode scraps and positive electrode residues produced by the lithium ion battery manufacturing process with lithium manganate as the positive electrode material to obtain the positive electrode sheet; Put the positive electrode piece into a ceramic crucible, and then place it in a box-type resistance furnace to raise the temperature of the furnace to 550 °C at a rate of 5 °C/min from room temperature and keep it for 20 min. Room temperature; take out the positive electrode sheet after roasting, put the positive electrode sheet into a container filled with water according to the ratio of the mass of the positive electrode sheet to the volume of water (g/mL) of 1:50 and stir with an electric stirrer at 50r/min Stir at a high speed for 20 minutes, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, sieve the mixture in the container with a 10-mesh sieve, the sieve is aluminum foil, and the sieve is a solution containing positive active substances; Rinse with water 3 times, and obtain aluminum foil by natural drying; filter the undersieve, and wash the supernatant with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, and then place it in a box-type resistance furnace Make furnace temperature rise to 600 ℃ and be incubated 30min with the heating rate of 5 ℃/min in, obtain waste lithium manganate powder; Waste lithium manganate powder and the potassium bisulfate obtained in step (6) of the present invention are by mass ratio ( g/g) at a ratio of 1:0.5, put it into a ceramic mortar, grind and mix it evenly, then put the ground mixture into a ceramic crucible and cover it with a ceramic cover and put it in a box-type resistance furnace at a temperature of 5°C/min. The heating rate is to raise the furnace temperature to 600°C and keep it warm for 30min; after the roasting is completed, the material in the crucible is leached with 50°C water under the condition of stirring for 20min at a solid-to-liquid ratio (g/mL) of 1:20; then Raise the temperature of the leachate to 98°C, slowly add 3.0mol/L potassium carbonate solution into the leachate to produce a precipitate, the obtained precipitate is filtered, washed, and dried, and the content of Li and Mn in the precipitate is analyzed, according to the molar ratio of lithium to manganese Add a certain amount of lithium carbonate to the sediment to meet the requirement of 0.525:1, then fully ball mill it in a planetary ball mill at a speed of 400r/min for 2 hours, then press it under a pressure of 5MPa, and put it into a clean ceramic crucible , keep the temperature at 450°C for 6 hours in an air atmosphere, then raise the temperature to 750°C for 20 hours, then slowly cool to room temperature, grind and grind the fired samples, and pass through a 400-mesh sieve to obtain the lithium manganate cathode material; filter the above steps The obtained solution was adjusted with concentrated sulfuric acid to make the pH value of the solution 1.0, and then crystallized in an evaporative crystallizer. The crystallization control conditions were vacuum degree of 0.015MPa and temperature of 120°C. The crystallized product was dried at 80°C and 2h to obtain potassium bisulfate .

Example 12

Collect positive electrode scraps and positive electrode residues produced by the lithium ion battery manufacturing process with lithium manganate as the positive electrode material to obtain the positive electrode sheet; Put the positive electrode piece into a ceramic crucible, and then place it in a box-type resistance furnace to raise the temperature of the furnace to 550 °C at a rate of 5 °C/min from room temperature and keep it for 20 min. Room temperature; take out the positive electrode sheet after roasting, put the positive electrode sheet into a container filled with water according to the ratio of the mass of the positive electrode sheet to the volume of water (g/mL) of 1:50 and stir with an electric stirrer at 50r/min Stir at a high speed for 20 minutes, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, sieve the mixture in the container with a 10-mesh sieve, the sieve is aluminum foil, and the sieve is a solution containing positive active substances; Rinse with water 3 times, and obtain aluminum foil by natural drying; filter the undersieve, and wash the supernatant with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, and then place it in a box-type resistance furnace Make furnace temperature rise to 600 ℃ and be incubated 30min with the heating rate of 5 ℃/min in, obtain waste lithium manganate powder; Waste lithium manganate powder and the potassium bisulfate obtained in step (6) of the present invention are by mass ratio ( g/g) at a ratio of 1:0.5, put it into a ceramic mortar, grind and mix it evenly, then put the ground mixture into a ceramic crucible and cover it with a ceramic cover and put it in a box-type resistance furnace at a temperature of 5°C/min. The heating rate is to raise the furnace temperature to 600°C and keep it warm for 10min; after the calcination, the material in the crucible is leached with 50°C water for 20min at a solid-to-liquid ratio (g/mL) of 1:20 under stirring conditions; then Raise the temperature of the leachate to 98°C, slowly add 3.0mol/L potassium carbonate solution into the leachate to produce a precipitate, the obtained precipitate is filtered, washed, and dried, and the content of Li and Mn in the precipitate is analyzed, according to the molar ratio of lithium to manganese Add a certain amount of lithium carbonate to the sediment to meet the requirement of 0.525:1, then fully ball mill it in a planetary ball mill at a speed of 400r/min for 2 hours, then press it under a pressure of 5MPa, and put it into a clean ceramic crucible , keep the temperature at 450°C for 6 hours in an air atmosphere, then raise the temperature to 750°C for 20 hours, then slowly cool to room temperature, grind and grind the fired samples, and pass through a 400-mesh sieve to obtain the lithium manganate cathode material; filter the above steps The obtained solution was adjusted with concentrated sulfuric acid to make the pH value of the solution 1.0, and then crystallized in an evaporative crystallizer. The crystallization control conditions were vacuum degree of 0.015MPa and temperature of 120°C. The crystallized product was dried at 80°C and 2h to obtain potassium bisulfate .

Example 13

Collect scrap lithium-ion batteries with lithium manganate as positive electrode material, place them in 1.0mol/L sodium hydroxide aqueous solution at room temperature for 2h discharge treatment; after discharge treatment, disassemble the scrap lithium-ion batteries to obtain Positive electrode sheet: according to the ratio (g/mL) of the mass of positive electrode sheet and the volume of ceramic crucible, positive electrode sheet is packed in the ratio of 1:15 in the ceramic crucible, is placed in box-type electric resistance furnace then and starts from room temperature with 5 ℃/mL The heating rate of min raised the furnace temperature to 550°C and kept it warm for 20 minutes, then cut off the power of the box-type resistance furnace, and cooled it to room temperature naturally; took out the roasted positive electrode sheet, and according to the ratio of the mass of the positive electrode sheet to the volume of water (g/ mL) is 1:50, put the positive electrode sheet into a container with water and stir it with an electric stirrer at a stirring speed of 50r/min for 20min, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, the mixture in the container Sieve with a 10-mesh sieve, the oversieve is aluminum foil, and the undersieve is a solution containing positive active substances; the aluminum foil is washed 3 times with water, and the aluminum foil is obtained by natural drying; the undersieve is subjected to suction filtration, and the oversieve is washed with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, then place it in a box-type resistance furnace to raise the furnace temperature to 600°C at a heating rate of 5°C/min and keep it for 30min to obtain waste manganese Lithium acid powder; put the waste lithium manganate powder and the purchased potassium bisulfate chemical product into a ceramic mortar in a mass ratio (g/g) of 1:0.9, fully grind and mix evenly, and then put the ground mixture into Put it into a ceramic crucible and cover it with a ceramic cover, put it into a box-type resistance furnace, raise the temperature of the furnace to 600°C at a heating rate of 5°C/min and keep it warm for 30min; The water at 45°C was leached for 30min at a solid-to-liquid ratio (g/mL) of 1:30; then the leachate was heated to 95°C, and 3.0mol/L potassium carbonate solution was slowly added to the leachate to produce a precipitate, which was filtered, After washing and drying, analyze the content of Li and Mn in the precipitate, add a certain amount of lithium carbonate to the precipitate according to the requirement that the molar ratio of lithium to manganese is 0.525:1, and then put it in the planetary ball mill at a speed of 400r/min Fully ball mill for 2 hours, then press it under the pressure of 5 MPa, put it into a clean ceramic crucible, keep the temperature at 450°C for 6 hours in the air atmosphere, then raise the temperature to 750°C and keep it for 20 hours, then slowly cool to room temperature, and the fired The sample is pulverized, ground, and passed through a 400-mesh sieve to obtain a lithium manganate positive electrode material; the solution obtained by filtering in the above steps is adjusted with concentrated sulfuric acid to make the pH value of the solution 1.0, and then crystallized in an evaporative crystallizer, and the crystallization control conditions are The vacuum degree is 0.015MPa, the temperature is 120°C, and the crystals are dried at 80°C for 2 hours to obtain potassium hydrogen sulfate.

Example 14

Collect scrap lithium-ion batteries with lithium manganate as positive electrode material, place them in 1.0mol/L sodium hydroxide aqueous solution at room temperature for 2h discharge treatment; after discharge treatment, disassemble the scrap lithium-ion batteries to obtain Positive electrode sheet: according to the ratio (g/mL) of the mass of positive electrode sheet and the volume of ceramic crucible, positive electrode sheet is packed in the ratio of 1:15 in the ceramic crucible, is placed in box-type electric resistance furnace then and starts from room temperature with 5 ℃/mL The heating rate of min raised the furnace temperature to 550°C and kept it warm for 20 minutes, then cut off the power of the box-type resistance furnace, and cooled it to room temperature naturally; took out the roasted positive electrode sheet, and according to the ratio of the mass of the positive electrode sheet to the volume of water (g/ mL) is 1:50, put the positive electrode sheet into a container with water and stir it with an electric stirrer at a stirring speed of 50r/min for 20min, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, the mixture in the container Sieve with a 10-mesh sieve, the oversieve is aluminum foil, and the undersieve is a solution containing positive active substances; the aluminum foil is washed 3 times with water, and the aluminum foil is obtained by natural drying; the undersieve is subjected to suction filtration, and the oversieve is washed with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, then place it in a box-type resistance furnace to raise the furnace temperature to 600°C at a heating rate of 5°C/min and keep it for 30min to obtain waste manganese Lithium acid powder; put the waste lithium manganate powder and the purchased potassium bisulfate chemical product into a ceramic mortar in a mass ratio (g/g) of 1:0.9, fully grind and mix evenly, and then put the ground mixture into Put it into a ceramic crucible and cover it with a ceramic cover and put it into a box-type resistance furnace to raise the temperature of the furnace to 650°C at a heating rate of 5°C/min and keep it warm for 30min; The water at 45°C was leached for 30min at a solid-to-liquid ratio (g/mL) of 1:30; then the leachate was heated to 95°C, and 3.0mol/L potassium carbonate solution was slowly added to the leachate to produce a precipitate, which was filtered, After washing and drying, analyze the content of Li and Mn in the precipitate, add a certain amount of lithium carbonate to the precipitate according to the requirement that the molar ratio of lithium to manganese is 0.525:1, and then put it in the planetary ball mill at a speed of 400r/min Fully ball mill for 2 hours, then press it under the pressure of 5 MPa, put it into a clean ceramic crucible, keep the temperature at 450°C for 6 hours in the air atmosphere, then raise the temperature to 750°C and keep it for 20 hours, then slowly cool to room temperature, and the fired The sample is pulverized, ground, and passed through a 400-mesh sieve to obtain a lithium manganate positive electrode material; the solution obtained by filtering in the above steps is adjusted with concentrated sulfuric acid to make the pH value of the solution 1.0, and then crystallized in an evaporative crystallizer, and the crystallization control conditions are The vacuum degree is 0.015MPa, the temperature is 120°C, and the crystals are dried at 80°C for 2 hours to obtain potassium hydrogen sulfate.

Example 15

Collect scrap lithium-ion batteries with lithium manganate as positive electrode material, place them in 1.0mol/L sodium hydroxide aqueous solution at room temperature for 2h discharge treatment; after discharge treatment, disassemble the scrap lithium-ion batteries to obtain Positive electrode sheet: according to the ratio (g/mL) of the mass of positive electrode sheet and the volume of ceramic crucible, positive electrode sheet is packed in the ratio of 1:15 in the ceramic crucible, is placed in box-type electric resistance furnace then and starts from room temperature with 5 ℃/mL The heating rate of min raised the furnace temperature to 550°C and kept it warm for 20 minutes, then cut off the power of the box-type resistance furnace, and cooled it to room temperature naturally; took out the roasted positive electrode sheet, and according to the ratio of the mass of the positive electrode sheet to the volume of water (g/ mL) is 1:50, put the positive electrode sheet into a container with water and stir it with an electric stirrer at a stirring speed of 50r/min for 20min, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, the mixture in the container Sieve with a 10-mesh sieve, the oversieve is aluminum foil, and the undersieve is a solution containing positive active substances; the aluminum foil is washed 3 times with water, and the aluminum foil is obtained by natural drying; the undersieve is subjected to suction filtration, and the oversieve is washed with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, then place it in a box-type resistance furnace to raise the furnace temperature to 600°C at a heating rate of 5°C/min and keep it for 30min to obtain waste manganese Lithium acid powder; put the waste lithium manganate powder and the purchased potassium bisulfate chemical product into a ceramic mortar in a mass ratio (g/g) of 1:0.9, fully grind and mix evenly, and then put the ground mixture into Put it into a ceramic crucible and cover it with a ceramic cover, put it into a box-type resistance furnace, raise the temperature of the furnace to 550°C at a heating rate of 5°C/min and keep it warm for 30min; The water at 45°C was leached for 30min at a solid-to-liquid ratio (g/mL) of 1:30; then the leachate was heated to 95°C, and 3.0mol/L potassium carbonate solution was slowly added to the leachate to produce a precipitate, which was filtered, After washing and drying, analyze the content of Li and Mn in the precipitate, add a certain amount of lithium carbonate to the precipitate according to the requirement that the molar ratio of lithium to manganese is 0.525:1, and then put it in the planetary ball mill at a speed of 400r/min Fully ball mill for 2 hours, then press it under the pressure of 5 MPa, put it into a clean ceramic crucible, keep the temperature at 450°C for 6 hours in the air atmosphere, then raise the temperature to 750°C and keep it for 20 hours, then slowly cool to room temperature, and the fired The sample is pulverized, ground, and passed through a 400-mesh sieve to obtain a lithium manganate positive electrode material; the solution obtained by filtering in the above steps is adjusted with concentrated sulfuric acid to make the pH value of the solution 1.0, and then crystallized in an evaporative crystallizer, and the crystallization control conditions are The vacuum degree is 0.015MPa, the temperature is 120°C, and the crystals are dried at 80°C for 2 hours to obtain potassium hydrogen sulfate.

Claims (5)

1. the method for reclaiming metal from the waste lithium ion battery of lithium manganate cathode material, it is characterized in that, its step is: Step (1): Place the collected scrap lithium-ion battery with lithium manganate as positive electrode material in 0.1-1.0mol/L sodium hydroxide aqueous solution at room temperature for 1-3h discharge treatment; after discharge treatment, Disassemble the scrapped lithium-ion battery to obtain the positive electrode sheet; collect the positive electrode scraps and positive electrode scraps generated during the manufacturing process of the lithium-ion battery with lithium manganate as the positive electrode material to obtain the positive electrode sheet; Step (2): Put the positive electrode sheet obtained in step (1) into the ceramic crucible according to the ratio of the mass of the positive electrode sheet to the volume of the ceramic crucible - g/mL is 1:10-1:15, Then place it in a resistance furnace from room temperature to raise the furnace temperature to 550°C at a rate of 5°C/min for 0.5-1h, then cut off the power of the resistance furnace, and cool it down to room temperature naturally; The ratio of the mass of the tablet to the volume of water-g/mL is 1:40-1:70. Put the positive electrode sheet into a container filled with water and stir for 5-30min. During the stirring process, the temperature of the water is 20-50°C. The stirring speed is 10-200r/min; after the stirring is stopped, sieve the mixture in the container with a 10-20 mesh screen, the sieve is aluminum foil, and the sieve is a solution containing positive active substances; the aluminum foil is washed with water for 1 -3 times, the aluminum foil was obtained by natural drying; the undersieve was subjected to suction filtration, and the filter was washed with water for 1-3 times to obtain the positive active material; Step (3): Put the positive electrode active material obtained in step (2) into a ceramic crucible, and then place it in a resistance furnace to raise the furnace temperature to 500-700°C at a heating rate of 5°C/min and keep it warm for 0.5-3h , to obtain waste lithium manganate powder; Step (4): Mix the waste lithium manganese oxide powder obtained in step (3) with potassium bisulfate at a mass ratio of -g/g of 1:0.2-1:1.2, then put them into a ceramic mortar and grind them thoroughly and mix them evenly , put the ground mixture into a ceramic crucible and cover it with a ceramic cover, then put it into a resistance furnace for roasting, raise the furnace temperature to 400-650°C at a heating rate of 3-10°C/min and keep it warm for 10-60min; Step (5): After the calcination, the material in the crucible is leached with water at 20-50°C under the condition of stirring, the leaching time is 5-30min, and the solid-liquid ratio-g/mL is 1:10-1:50 ; Then heat the leachate to 95-98°C, slowly add 1.0-3.0mol/L potassium carbonate solution to the leachate, then filter, wash and dry the filter residue, analyze the content of Li and Mn in the filter residue, according to the molar ratio of lithium to manganese To meet the requirement of 0.525:1, add lithium carbonate to the filter residue, and then fully ball mill it in a ball mill, then press it under a pressure of 0.1-100MPa, put it into a clean ceramic crucible, and keep it in an air atmosphere at a constant temperature of 450°C for 4- After 7 hours, the temperature was raised to 750°C for 20 hours, and then slowly cooled to room temperature. The fired samples were pulverized, ground, and passed through a 400-mesh sieve to obtain lithium manganate cathode materials; Step (6): Filter the solution obtained in step (5) to adjust the composition with concentrated sulfuric acid so that the pH of the solution is 0.5-1.0, and then crystallize in an evaporation crystallizer. The crystallization control conditions are vacuum degree 0.012-0.015MPa, temperature 120 -140°C, dry the crystals at 50-80°C for 0.2-3h to obtain potassium hydrogen sulfate, and return the obtained potassium hydrogen sulfate for use in step (4). 2. The method for recovering metals from waste lithium ion batteries of lithium manganate cathode material according to claim 1, characterized in that the potassium hydrogen sulfate described in step (4) is: potassium hydrogen sulfate chemical product or step ( 6) Potassium hydrogen sulfate obtained in 6) or the mixture formed by mixing the two in any proportion. 3. The method for recovering metal from the waste lithium ion battery of lithium manganate positive electrode material according to claim 1, characterized in that the mixing ratio of waste lithium manganate powder and potassium bisulfate described in step (4) is : The mass ratio -g/g is 1:0.2-1:1.2. 4. The method for recovering metals from waste lithium-ion batteries of lithium manganate cathode material according to claim 1, characterized in that the process conditions for roasting in a resistance furnace in step (4) are: the heating rate is 3-10°C /min, the calcination temperature is 400-650°C, and the holding time is 10-60min. 5. The method for recovering metals from waste lithium ion batteries as lithium manganate cathode material according to claim 1, characterized in that the ball milling time in step (5) is 0.5-2h, and the rotation speed is 200-500r/min.